KR101153387B1 - Rubber composition for tire tread and tire manufactured by using the same - Google Patents

Abstract

The present invention relates to a rubber composition for tire treads and a tire manufactured using the same, and provides a rubber composition for tire treads including raw material rubber and silica nanotubes.

The rubber tread rubber composition is advantageous in terms of processability, has excellent tensile strength, and improves braking performance on a wet road surface and fuel economy of an automobile.

Silica nanotube, nanotube, SNT, reinforcing filler, silica, carbon black, coupling agent, vulcanizing agent, vulcanization accelerator, zinc oxide, stearic acid, anti-aging agent

Description

RUBBER COMPOSITION FOR TIRE TREAD AND TIRE MANUFACTURED BY USING THE SAME

The present invention relates to a rubber tread rubber composition and a tire manufactured using the same, which is advantageous in terms of processability, has excellent tensile strength, improves braking performance on wet road surfaces, and improves fuel economy of an automobile, and It relates to a tire manufactured using the same.

In accordance with recent eco-friendly policies, the tire industry is interested in developing low-fuel tires by reducing tire rolling resistance. In addition, techniques for using silica and eco-friendly fillers in tire tread rubber to achieve this are constantly being developed.

 Materials used as environmentally friendly fillers for the tire tread rubber are typically carbon black and silica, in addition to nanoclays, clam shell pulverized, or cellulose.

In the case of silica, since the surface chemical property is polar, it is not easy to disperse in non-polar rubber, which is disadvantageous in terms of processability. Thus, a coupling agent is used to solve this problem. The coupling agent reacts with the silanol group of the silica to change the surface chemical property of the silica to nonpolarity, thereby facilitating mixing with the rubber. However, the coupling agent is an expensive material and is disadvantageous in terms of cost as well as a problem in that ethanol is generated when reacted with silica and volatilized during the process. Moreover, when increasing the content of silica to improve the braking performance of the tire, the workability problem may be more serious.

An object of the present invention is to provide a rubber composition for tire treads that is advantageous in terms of workability, excellent in tensile strength, and can improve braking performance on a wet road surface and fuel economy of an automobile.

Another object of the present invention is to provide a tire manufactured using the rubber tread rubber composition.

In order to achieve the above object, the rubber composition for a tire tread according to an embodiment of the present invention includes a raw material rubber, and silica nanotubes.

The tire tread rubber composition may include 100 parts by weight of raw material rubber, 0 to 100 parts by weight of reinforcing filler, and 5 to 30 parts by weight of silica nanotubes.

The reinforcing filler may be any one selected from the group consisting of carbon black, silica, and combinations thereof.

The silica nanotubes may have an outer diameter of 10 to 30 nm, an inner diameter of 1 to 10 nm, and a length of 10 to 100 nm.

The silica nanotubes may have a BET surface area of 100 to 1000 m ² / g, a pore volume of 0.1 to 10 cm ³ / g, and a pore size of 1 to 50 nm.

A tire according to another embodiment of the present invention is manufactured using the rubber composition for the tire tread.

Hereinafter, the present invention will be described in more detail.

The tire tread rubber composition includes raw material rubber and silica nanotubes.

The raw rubber may be any one selected from the group consisting of natural rubber, synthetic rubber, and combinations thereof.

The natural rubber may be general natural rubber or modified natural rubber.

The general natural rubber may be used as long as it is known as natural rubber, and the origin and the like are not limited. The natural rubber contains cis-1,4-polyisoprene as a main agent, but may also include trans-1,4-polyisoprene depending on the required properties. Therefore, the natural rubber includes, in addition to the natural rubber containing cis-1,4-polyisoprene as a main agent, for example, a natural containing trans-1,4-isoprene as a main agent such as a balata, which is a kind of rubber of South American sapotagua. Rubber may also be included.

The modified natural rubber means a modified or refined general natural rubber. For example, the modified natural rubber may include epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, and the like.

Synthetic rubber is styrene butadiene rubber (SBR), modified styrene butadiene rubber, butadiene rubber (BR), modified butadiene rubber, chloro sulfonated polyethylene rubber, epichlorohydrin rubber, fluorine rubber, silicone rubber, nitrile rubber, hydrogenated Nitrile Rubber, Nitrile Butadiene Rubber (NBR), Modified Nitrile Butadiene Rubber, Chlorinated Polyethylene Rubber, Styrene Ethylene Butylene Styrene (SEBS) Rubber, Ethylene Propylene Rubber, Ethylene Propylene Diene (EPDM) Rubber, Hypalon Rubber, Chloroprene Rubber, ethylene vinyl acetate rubber, acrylic rubber, hydrin rubber, vinyl benzyl chloride styrene butadiene rubber, bromomethyl styrene butyl rubber, maleic acid styrene butadiene rubber, carboxylic acid styrene butadiene rubber, epoxy isoprene rubber, maleic acid ethylene propylene rubber, carboxylic Acid Nitrile Butadiene High Radish, brominated polyisobutyl isoprene-co-paramethyl styrene (brominated polyisobutyl isoprene-co-paramethyl styrene, BIMS) and combinations thereof may be any one selected from the group.

In particular, the raw material rubber may be preferably used any one selected from styrene butadiene rubber, butadiene rubber and combinations thereof. In addition, the raw rubber may be used to include 75 to 90 parts by weight of styrene butadiene rubber and 10 to 25 parts by weight of butadiene rubber.

If the content of the styrene butadiene rubber is less than 75 parts by weight may have a problem in the dispersion of the silica nanotubes, if more than 90 parts by weight may have a problem in the wear resistance. If the content of the butadiene rubber is less than 10 parts by weight may have a problem in the wear resistance, if more than 25 parts by weight may have a problem in the dispersion of the silica nanotubes.

The silica nanotubes are a kind of metal oxide nanotubes, and are added to and dispersed in the rubber tread rubber composition to reduce wear of a polymer material and to reduce braking distance due to nanoprotrusion characteristics. It acts as a reinforcing filler.

The silica nanotubes may have an outer diameter of 10 to 30 nm, an inner diameter of 1 to 10 nm, and a length of 10 to 100 nm, preferably an outer diameter of 10 to 20 nm, an inner diameter of 3 to 5 nm, and a length of 50 to 80 nm. However, the present invention is not limited thereto.

When the outer diameter of the silica nanotubes are 10 to 30 nm, the inner diameter is 1 to 10 nm, and the length is 10 to 100 nm, it is preferable in terms of reinforcement of rubber. Problems may arise.

In addition, the silica nanotube has a BET surface area of 100 to 1000 m ² / g, a pore volume of 0.1 to 10 cm ³ / g, the pore size may be 1 to 50 nm, preferably BET surface area of 700 to 900 m ² / g The pore volume is 3 to 5 cm ³ / g, the pore size may be 20 to 30nm, but the present invention is not limited thereto.

The silica nanotubes have a BET surface area of 100 to 1000 m ² / g, a pore volume of 0.1 to 10 cm ³ / g, and a pore size of 1 to 50 nm is preferable in terms of reinforcement. May occur.

The silica nanotubes may be included in 5 to 30 parts by weight based on 100 parts by weight of the raw material rubber. When the content of the silica nanotube is less than 5 parts by weight, the reinforcing effect may be insignificant, and when the content exceeds 30 parts by weight, processing may be difficult. The silica nanotubes can improve the physical properties of the rubber compound by increasing the reinforcement of the rubber composition even with a small amount, improve the fuel efficiency of the car by reducing the rolling resistance in terms of tire performance, and improve the braking performance on the wet road surface Let's do it.

The silica nanotubes may be prepared using various methods of manufacturing metal oxide nanotubes such as a template method, a sol-gel method, or a hydrothermal method, but the method of manufacturing the silica nanotubes is not particularly limited in the present invention.

In the case of using the sol-gel method, TEOS can be hydrolyzed in the presence of ammonia and D, L-tartaric acid to obtain silica nanotubes. In addition, mesoporous silica nanotubes can be prepared by subjecting mesoporous silica material to hydrothermal ammonia. Using this method, it is possible to simultaneously reconstruct the pore size of the silica nanotubes, the regularity of the nanochannels, and the shape of the mesoporous material. This reconstituted product forms very well aligned silica nanotubes. In addition, when grown using a surfactant, very long silica nanotubes can be obtained.

The tire tread rubber composition may further include a reinforcing filler in addition to the silica nanotubes. The filler may be any one selected from the group consisting of silica, carbon black, calcium carbonate, clay (aluminum hydrated silica), aluminum hydroxide, lignin, silicate, talc and combinations thereof.

The silica has a nitrogen adsorption specific surface area (N ₂ SA, nitrogen surface area per gram) of 100 to 180 m 2 / g, CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of 110 to 170 m 2 / g used It can be used, but the present invention is not limited thereto.

The silica can be used both wet or dry method, and commercially available products such as ultra-sil VN2 (manufactured by Degussa Ag), ultra-sil VN3 (manufactured by Degussa Ag), Z1165MP (manufactured by Rhodia) or Z165GR (manufactured by Rhodia) Can be.

The silica may be included in an amount of 0 to 100 parts by weight, and 50 to 80 parts by weight based on 100 parts by weight of the raw material rubber. When the content of the silica exceeds 100 parts by weight, the workability of the tire may be lowered. When the content of the silica is less than 50 parts by weight, the reinforcing effect may be insignificant, and when the content of the silica exceeds 80 parts by weight, wear performance may be reduced. have.

The carbon black may have a nitrogen adsorption specific surface area of 30 to 300 m ² / g, preferably 110 to 150 m ² / g, and more preferably 118 to 122 m ² / g. When the nitrogen adsorption specific surface area of the carbon black exceeds 300 m ² / g, there is an advantageous surface for the reinforcement of cutting resistance and chipping resistance, but the processability of the rubber composition for tires may be detrimental, and when less than 30 m ² / g is used. The reinforcement by the carbon black filler may be reduced.

The carbon black may have a DBP (n-dibutyl phthalate) oil absorption of 60 to 180cc / 100g, preferably 110 to 120cc / 100g, and more preferably 124 to 128cc / 100g. When the DBP oil absorption of the carbon black exceeds 180cc / 100g, the processability of the tread rubber composition may be lowered. If the DBP oil absorption of the carbon black is less than 60cc / 100g, the reinforcing performance of the carbon black as a filler may be detrimental.

Representative examples of the carbon black are N110, N121, N134, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582 , N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990, N991 and the like.

The carbon black may be included in an amount of 0 to 100 parts by weight, and 50 to 80 parts by weight based on 100 parts by weight of the raw material rubber. When the content of the carbon black exceeds 100 parts by weight, the workability of the rubber tread rubber composition may be lowered. When the content of the carbon black is less than 50 parts by weight, the reinforcing effect may be insignificant.

The tire tread rubber composition may optionally further include various additives such as additional vulcanizing agents, vulcanization accelerators, vulcanization accelerators, coupling agents, anti-aging agents and softeners. The various additives can be used as long as it is commonly used in the field of the present invention, the content thereof is not particularly limited, depending on the compounding ratio used in the conventional tire tread rubber composition.

As the vulcanizing agent, metal oxides such as sulfur vulcanizing agents, organic peroxides, resin vulcanizing agents, and magnesium oxide can be used.

The sulfur-based vulcanizing agents include inorganic vulcanizing agents such as powdered sulfur (S), insoluble sulfur (S), precipitated sulfur (S) and colloidal sulfur, tetramethylthiuram disulfide (TMTD) and tetraethyl. Organic vulcanizing agents such as tetraethyltriuram disulfide (TETD) and dithiodimorpholine can be used. Specifically, as the sulfur vulcanizing agent, a vulcanizing agent which produces elemental sulfur or sulfur, for example, amine disulfide, polymer sulfur, or the like can be used.

The organic peroxide may be benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di ( t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3- Bis (t-butylperoxypropyl) benzene, di-t-butylperoxy-diisopropylbenzene, t-butylperoxybenzene, 2,4-dichlorobenzoyl peroxide, 1,1-dibutylperoxy-3 Any one selected from the group consisting of, 3,5-trimethylsiloxane, n-butyl-4,4-di-t-butylperoxyvalerate and combinations thereof can be used.

The vulcanizing agent is preferably included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the raw rubber, in that the raw rubber is less sensitive to heat and chemically stable.

The vulcanization accelerator refers to an accelerator that promotes the rate of vulcanization or promotes delay in the initial vulcanization stage.

Examples of the vulcanization accelerator include sulfenamide, thiazole, thiuram, thiourea, old anidine, dithiocarbamic acid, aldehyde-amine, aldehyde-ammonia, imidazoline, xanthate and these Any one selected from the group consisting of can be used.

Examples of the sulfenamide-based vulcanization accelerators include N-cyclohexyl-2-benzothiazylsulfenamide (CBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), and N, N-dicyclohexyl. Any selected from the group consisting of -2-benzothiazylsulfenamide, N-oxydiethylene-2-benzothiazylsulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide and combinations thereof The sulfenamide type compound of can be used.

Examples of the thiazole vulcanization accelerators include 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), sodium salt of 2-mercaptobenzothiazole and zinc salt of 2-mercaptobenzothiazole. , Copper salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-di Any thiazole compound selected from the group consisting of ethyl 4-morpholinothio) benzothiazole and combinations thereof can be used.

Examples of the thiuram-based vulcanization accelerators include tetramethyl thiuram disulfide (TMTD), tetraethyl thiuram disulfide, tetramethyl thiuram monosulfide, dipentamethylene thiuram disulfide, dipentamethylene thiuram monosulfide and dipentamethylene. Any thiuram-based compound selected from the group consisting of thiuram tetrasulfide, dipentamethylene thiuram hexasulfide, tetrabutyl thiuram disulfide, pentamethylene thiuram tetrasulfide, and combinations thereof can be used.

As the thiourea vulcanization accelerator, for example, thiocarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea, and any combination thereof is selected from the group of thiourea Compounds can be used.

As the guanidine-based vulcanization accelerator, for example, any one guanidine-based compound selected from the group consisting of diphenylguanidine, diorthotolylguanidine, triphenylguanidine, orthotolylbiguanide, diphenylguanidine phthalate, and combinations thereof can be used. Can be.

Examples of the dithiocarbamic acid-based vulcanization accelerators include ethylphenyldithiocarbamate zinc, butylphenyldithiocarbamate zinc, sodium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, Zinc dibutyldithiocarbamate, zinc diamyldithiocarbamate, zinc dipropyldithiocarbamate, zinc salt of pentamethylenedithiocarbamate and piperidine, hexadecylisopropyldithiocarbamate zinc, octadecyl Isopropyldithiocarbamate zinc dibenzyldithiocarbamate zinc, sodium diethyldithiocarbamate, pentamethylenedithiocarbamate piperidine, dimethyldithiocarbamate selenium, diethyldithiocarbamate tellurium, dia One dithiocarbamic acid compound selected from the group consisting of cadmium didicarbamate and combinations thereof can be used.

The aldehyde-amine-based or aldehyde-ammonia based vulcanization accelerator, for example, acetaldehyde-aniline reactant, butylaldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde-ammonia reactant and combinations thereof -Amine based or aldehyde-ammonia based compounds can be used.

As said imidazoline type vulcanization accelerator, imidazoline type compounds, such as 2-mercaptoimidazoline, can be used, for example, As said xanthate type vulcanization accelerator, xanthate type, such as zinc dibutyl xanthogenate Compounds can be used.

The vulcanization accelerator may be included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the raw rubber in order to maximize productivity and rubber properties by promoting the vulcanization rate.

The vulcanization accelerator is a compounding agent used in combination with the vulcanization accelerator to complete its promoting effect. Any one selected from the group consisting of inorganic vulcanization accelerators, organic vulcanization accelerators and combinations thereof can be used. .

As the inorganic vulcanization accelerating aid, any one selected from the group consisting of zinc oxide (ZnO), zinc carbonate, magnesium oxide (MgO), lead oxide, potassium hydroxide and combinations thereof may be used have. The organic vulcanization accelerator is selected from the group consisting of stearic acid, zinc stearate, palmitic acid, linoleic acid, oleic acid, lauric acid, dibutyl ammonium oleate, derivatives thereof, and combinations thereof. You can use either one.

In particular, the zinc oxide and the stearic acid may be used together as the vulcanization accelerator, in which case the zinc oxide is dissolved in the stearic acid to form an effective complex with the vulcanization accelerator, thereby releasing advantageous sulfur during the vulcanization reaction. It facilitates the crosslinking reaction of the rubber.

When the zinc oxide and the stearic acid are used together, it may be used in an amount of 1 to 10 parts by weight and 1 to 10 parts by weight based on 100 parts by weight of the raw rubber, respectively, to serve as a suitable vulcanization accelerator.

The coupling agent is used to improve the dispersibility of silica, and includes a sulfide silane compound, a mercapto silane compound, a vinyl silane compound, an amino silane compound, a glycidoxy silane compound, a nitro silane compound, and a chloro silane. Any one selected from the group consisting of a compound, a methacrylic silane compound, and a combination thereof can be used.

The sulfide-based silane compound may be bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (4-triethoxysilylbutyl) tetrasulfide, bis (3-tri Methoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, bis (4-trimethoxysilylbutyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (2 -Triethoxysilylethyl) trisulfide, bis (4-triethoxysilylbutyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (2-trimethoxysilylethyl) trisulfide, bis (4-trimethoxysilylbutyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) disulfide, bis (4-triethoxysilylbutyl) disulfide, bis ( 3-trimethoxysilylpropyl) disulfide, bis (2-trimethoxy Sisylethyl) disulfide, bis (4-trimethoxysilylbutyl) disulfide, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethyl Thiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N, N-dimethylthiocarbamoyl tetra sulfide, 3-trimethoxysilyl Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide and combinations thereof It may be any one selected from the group consisting of.

The mercapto silane compound is 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane and combinations thereof It may be any one selected from the group consisting of. The vinyl silane compound may be any one selected from the group consisting of ethoxysilane, vinyltrimethoxysilane, and combinations thereof. The amino silane compound is 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltri It may be any one selected from the group consisting of methoxysilane and combinations thereof.

The glycidoxy silane compounds include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane And combinations thereof may be any one selected from the group consisting of. The nitro silane compound may be any one selected from the group consisting of 3-nitropropyltrimethoxysilane, 3-nitropropyltriethoxysilane, and combinations thereof. The chloro-based silane compound is selected from the group consisting of 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, and combinations thereof. It can be any one.

The methacrylic silane compound is any one selected from the group consisting of γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl methyldimethoxysilane, γ-methacryloxypropyl dimethyl methoxysilane, and combinations thereof Can be.

The coupling agent may be included in an amount of 0 to 20 parts by weight based on 100 parts by weight of the raw material rubber to improve dispersibility of the silica.

The softener is added to the rubber composition to impart plasticity to the rubber to facilitate processing or to lower the hardness of the vulcanized rubber, and refers to oils and other materials used in rubber compounding or rubber production. The softener may be any one selected from the group consisting of petroleum oil, vegetable oil and combinations thereof, but the present invention is not limited thereto.

The petroleum oil may be any one selected from the group consisting of paraffinic oil, naphthenic oil, aromatic oil, and combinations thereof.

Representative examples of the paraffinic oil include P-1, P-2, P-3, P-4, P-5, and P-6 of Michang Oil, Inc. A representative example of the naphthenic oil is Michang oil. N-1, N-2, N-3, etc. of the corporation | Co., Ltd. are mentioned, As a representative example of the said aromatic oil, A-2, A-3, etc. of Michang Oil Corporation are mentioned.

However, it is known that cancer is more likely to occur when the content of polycyclic aromatic hydrocarbons (hereinafter referred to as "PAHs") included in the aromatic oils is 3% by weight or more with the recent increase of environmental awareness. , TDAE (treated distillate aromatic extract) oil, mild extraction solvate (MES) oil, residual aromatic extract (RAE) oil or heavy naphthenic oil can be preferably used.

In particular, the oil used as the softener has a total content of PAHs component of 3% by weight or less, a kinematic viscosity of 95 ° C or more (210 ° F SUS), an aromatic component in the softener of 15 to 25% by weight, naphthenic TDAE oils with 27 to 37% by weight and 38 to 58% by weight of paraffinic components can be preferably used.

The TDAE oil is advantageous in terms of environmental factors such as the low temperature characteristics of the tire tread including the TDAE oil, fuel efficiency, and the likelihood of causing cancer of PAHs.

The plant oils include castor oil, cottonseed oil, linseed oil, canola oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, pine tar, tall oil, corn oil, rice bran oil, safflower oil, sesame oil, olive oil, sunflower oil, palm kernel oil, camellia oil It may be used any one selected from the group consisting of jojoba oil, macadamia nut oil, saflower flower oil, tung oil and combinations thereof.

The softener is preferably used in an amount of 0 to 70 parts by weight with respect to 100 parts by weight of the raw material rubber in terms of improving the processability of the raw material rubber.

The anti-aging agent is an additive used to stop the chain reaction in which the tire is automatically oxidized by oxygen. As the anti-aging agent, any one selected from the group consisting of amine-based, phenol-based, quinoline-based, imidazole-based, carbamic acid metal salts, waxes, and combinations thereof may be appropriately selected.

Examples of the amine antioxidant include N-phenyl-N '-(1,3-dimethyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-diaryl-p-phenylenediamine, N-phenyl-N ' Any one selected from the group consisting of -cyclohexyl p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine, and combinations thereof can be used.

The phenolic anti-aging agent is phenolic 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-isobutylidene-bis (4,6-dimethylphenol), 2 Any one selected from the group consisting of, 6-di-t-butyl-p-cresol and combinations thereof can be used.

As the quinoline anti-aging agent, 2,2,4-trimethyl-1,2-dihydroquinoline and derivatives thereof may be used, and specifically 6-ethoxy-2,2,4-trimethyl-1,2-di Hydroquinoline, 6-anilino-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline and combinations thereof Any one selected from the group can be used.

Wax hydrocarbon may be preferably used as the wax.

The anti-aging agent may be N- (1,3-dimethylbutyl) -N-phenyl-p-phenylenediamine (N- (1,3-Dimethybutyl) -N-phenyl-p-phenylenediamine, 6PPD), N-phenyl n-isopropyl-p-phenylenediamine (3PPD) and poly (2,2,4-trimethyl-1,2-dihydroquinoline (Poly (2,2) , 4-trimethyl-1,2-dihydroquinoline, RD) and a combination thereof can be preferably used.

The anti-aging agent has a high solubility in rubber in addition to the anti-aging action, is low in volatility, inert to rubber, and does not inhibit vulcanization. It may be included in parts by weight.

The rubber composition for a tire tread can be produced through a conventional two-step continuous manufacturing process. That is, during the finishing step in which the first step of thermomechanical treatment or kneading at a maximum temperature ranging from 110 to 190 ° C., preferably from 130 to 180 ° C. (called “non-production” step) and the crosslinking system are mixed, Typically can be prepared in a suitable mixer using a second step (called "production" step) of mechanical treatment at a low temperature of less than 110 ° C, for example 40 to 100 ° C, but the invention is not limited thereto. .

The rubber composition for the tire tread is not limited to the tread (tread cap and tread base), and may be included in various rubber components constituting the tire. Such rubber components include sidewalls, sidewall inserts, apex, chafers, wire coats or innerliners, and the like.

A tire according to another embodiment of the present invention is manufactured using the rubber tread rubber composition. The method of manufacturing a tire using the tire tread rubber composition may be applied to any method conventionally used for the production of tires, and thus, detailed description thereof will be omitted.

The tire may be a passenger car tire, a racing tire, an airplane tire, a farm tire, an off-the-road tire, a truck tire or a bus tire. In addition, the tire may be a radial tire or a bias tire, and is preferably a radial tire.

The rubber composition for tire treads of the present invention is advantageous in terms of processability, has excellent tensile strength, and improves braking performance on wet road surfaces and fuel economy of automobiles.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[Production Example: Production of Rubber Composition]

To prepare a tire tread rubber composition according to the Example and Comparative Example using the composition shown in Table 1. Preparation of the tire tread rubber composition was in accordance with a conventional method for producing a tire tread rubber composition.

In Examples and Comparative Examples, the raw material rubber was a mixed rubber of styrene-butadiene rubber and butadiene rubber, and silica and silica nanotubes were used together as a reinforcing filler in Examples. In addition, in the Examples and Comparative Examples, 15 parts by weight of the silane coupling agent, 2 parts by weight of zinc oxide, 1 part by weight of stearic acid, 2 parts by weight of sulfur, and 1.8 parts by weight of vulcanization accelerator were used.

[Table 1] (Unit: parts by weight)

Example 1 Example 2 Example 3 Comparative Example 1 SBR ¹⁾ 123.75
(90) 123.75
(90) 123.75
(90) 123.75
(90) BR ²⁾ 10 10 10 10 Silica ³⁾ 75 65 50 80 Coupling Agent ⁴⁾ 12 11 8 15 Silica Nanotubes ⁵⁾ 5 15 30  - Zinc oxide ⁶⁾ 2 2 2 2 Stearic acid ⁷⁾ One One One One Vulcanizing agent ⁸⁾ 2 2 2 2 Vulcanization accelerator ⁹⁾ 1.8 1.8 1.8 1.8

1) SBR: SBR1712 ^® (LG Chemical), containing 37.5 parts by weight of processed oil, based on 100 parts by weight of pure rubber.

2) BR: BR1208 ^® (LG Chemistry)

3) Silica: U7000Gr ^® (Evonik)

4) Coupling Agent: X50S ^® (Evonik)

5) Silica nanotubes: outer diameter is 10-30 nm, inner diameter is 1-10 nm, length is 10-100 nm, BET surface area is 100-1000 m ² / g, pore volume is 0.1-10 cm ³ / g, pores The size is 1-50 nm.

6) Zinc Oxide: Zinc Oxide (Hanil Chemical)

7) Stearic Acid: Stearic Acid (LG Chemistry)

8) Vulcanizing agent: Sulfur (Ground Sulfur)

9) Vulcanization accelerator: N-cyclohexyl-2-benzothiazylsulfenamide (Lanxess)

Experimental Example: Measurement of Properties of Prepared Rubber Composition

The physical properties of the rubber specimens prepared in Examples and Comparative Examples were measured, and the results are shown in Table 2 below.

[Table 2]

Example 1 Example 2 Example 3 Comparative Example 1 Unvulcanized Properties Mooney viscosity 79 77 73 83 Tensile Properties Hardness 72 70 67 73 100% modulus
(kgf / cm ² ) 32 36 39 30 300% modulus
(kgf / cm ² ) 122 129 137 115 Elongation (%) 458 450 424 480 Tensile strength (kgf / cm ² ) 212 220 247 203 Viscoelastic properties 0 ℃ tanδ 0.556 0.582 0.597 0.532 60 ℃ tanδ 0.176 0.129 0.102 0.193

(1) Mooney Viscosity (ML1 + 4, 125 ° C): Measured using a Mooney MV2000 (Alpha Technology) instrument at Large Rotor, preheat 1 minute, rotor run time 4 minutes, temperature 125 ° C It was. Mooney viscosity means that the higher the value, the greater the viscosity of the rubber, and indicates that the workability is disadvantageous.

(2) Tensile Properties: Measured using an Instron tester according to ASTM D412 test method.

(3) Viscoelastic properties: Using a DMTS (Dynamic Material Testing System) tester was measured with a temperature sweep from -60 ℃ to 80 ℃ in 10Hz, static strain 5%, dynamic strain 0.5% conditions. In this case, the higher the 0 ° C tanδ value, the better the braking performance on the wet road surface, and the lower the 60 ° C tanδ value, the lower the rolling resistance.

Referring to Table 2, the rubber composition for tire treads prepared in Examples 1 to 3 shows a slightly lower Mooney viscosity than the rubber composition for tire treads prepared in Comparative Example 1. Therefore, it can be seen that the rubber composition for tire treads prepared in Examples 1 to 3 has advantageous processability as compared with the rubber composition for tire treads prepared in Comparative Example 1.

In the case of tensile properties, the physical properties of Examples 1 to 3 show a general tendency to improve when compared with the physical properties of Comparative Example 1. This can be seen that in Examples 1 to 3, the reinforcement of the silica nanotubes is superior to that of silica, indicating higher tensile strength than Comparative Example 1. In addition, it can be seen that as the amount of silica nanotubes increases, the tensile strength also tends to increase.

In the case of viscoelastic properties, it can be seen that Examples 1 to 3 have a slightly higher 0 ° C. tanδ value than that of Comparative Example 1, thereby improving braking performance on wet road surfaces. In addition, in the case of Examples 1 to 3 has a lower tan ℃ value than the case of Comparative Example 1 it can be seen that the tire's rolling resistance is lowered to improve the fuel economy of the car.

Taken together, the results of the silica nanotubes are advantageous in terms of processability compared to the case of using only silica, and the tensile strength can be improved. In addition, the braking performance on the wet road surface and the fuel economy of the automobile can be improved.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (6)

Raw material rubber, and Silica nano tube Including, The silica nanotubes have an outer diameter of 10 to 30 nm, an inner diameter of 1 to 10 nm, and a length of 10 to 100 nm. Rubber composition for tire tread. The method of claim 1, The tire tread rubber composition 100 parts by weight of raw rubber, 0 to 100 parts by weight of reinforcing fillers, and 5 to 30 parts by weight of silica nanotubes A rubber composition for a tire tread comprising a. 3. The method of claim 2, The reinforcing filler is any one selected from the group consisting of carbon black, silica, and combinations thereof. delete The method of claim 1, The silica nanotube has a BET surface area of 100 to 1000 m ² / g, pore volume of 0.1 to 10 cm ³ / g, the pore size is 1 to 50 nm rubber composition for tire tread. A tire manufactured using the rubber composition for tire tread according to any one of claims 1 to 3 and 5.